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Depends on what type of work you want to do and who for. PHP is in very wide use on all sorts of web sites/applications. .NET is very popular with Fortune 500 type companies, along with JAVA/JSP. That being said, if you choose to go the .NET route, I'd learn C# instead of ASP, myself. (Personally, I'm doing pretty well working with PHP. )

If you are familiar with C,C++ then I would like to suggest to prefer PHP. It is quite really helpful to develop the web application. You can have a lot of function or features in the web application using PHP. It is easy to learn as I prefer.